US3591645A - Process for preparing a halogenated aromatic - Google Patents
Process for preparing a halogenated aromatic Download PDFInfo
- Publication number
- US3591645A US3591645A US730589A US3591645DA US3591645A US 3591645 A US3591645 A US 3591645A US 730589 A US730589 A US 730589A US 3591645D A US3591645D A US 3591645DA US 3591645 A US3591645 A US 3591645A
- Authority
- US
- United States
- Prior art keywords
- palladium
- aromatic hydrocarbon
- chloride
- reaction
- millimols
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 125000003118 aryl group Chemical group 0.000 title description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 33
- 239000002184 metal Substances 0.000 abstract description 33
- -1 BROMO AROMATIC HYDROCARBON Chemical class 0.000 abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 19
- 150000001875 compounds Chemical class 0.000 abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 14
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 13
- 239000010941 cobalt Substances 0.000 abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 abstract description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 abstract description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 8
- 229910052703 rhodium Inorganic materials 0.000 abstract description 8
- 239000010948 rhodium Substances 0.000 abstract description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 229910052762 osmium Inorganic materials 0.000 abstract description 7
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052697 platinum Inorganic materials 0.000 abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 7
- 229910052718 tin Inorganic materials 0.000 abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052787 antimony Inorganic materials 0.000 abstract description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 6
- 229940006460 bromide ion Drugs 0.000 abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 abstract description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052804 chromium Inorganic materials 0.000 abstract description 6
- 239000011651 chromium Substances 0.000 abstract description 6
- 229910052741 iridium Inorganic materials 0.000 abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052753 mercury Inorganic materials 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 229940005654 nitrite ion Drugs 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000012442 inert solvent Substances 0.000 abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 59
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- 238000000034 method Methods 0.000 description 44
- 238000006243 chemical reaction Methods 0.000 description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 36
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- 229910052763 palladium Inorganic materials 0.000 description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- 150000003839 salts Chemical class 0.000 description 23
- 239000000047 product Substances 0.000 description 18
- 239000010949 copper Substances 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 12
- 229910002651 NO3 Inorganic materials 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 241001579016 Nanoa Species 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- BYNPVFHVZRNRQD-UHFFFAOYSA-N acetic acid;benzene Chemical compound CC(O)=O.C1=CC=CC=C1 BYNPVFHVZRNRQD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 229940076286 cupric acetate Drugs 0.000 description 2
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 2
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 2
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 2
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid group Chemical group C(CCCCCC)(=O)O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- CJPVPOYTTALCNX-UHFFFAOYSA-N (2-chlorophenyl) acetate Chemical compound CC(=O)OC1=CC=CC=C1Cl CJPVPOYTTALCNX-UHFFFAOYSA-N 0.000 description 1
- KEUPLGRNURQXAR-UHFFFAOYSA-N (4-chlorophenyl) acetate Chemical compound CC(=O)OC1=CC=C(Cl)C=C1 KEUPLGRNURQXAR-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- PAGZTSLSNQZYEV-UHFFFAOYSA-L 2,2-dimethylpropanoate;palladium(2+) Chemical compound [Pd+2].CC(C)(C)C([O-])=O.CC(C)(C)C([O-])=O PAGZTSLSNQZYEV-UHFFFAOYSA-L 0.000 description 1
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 1
- FQHYQCXMFZHLAE-UHFFFAOYSA-N 25405-85-0 Chemical compound CC1(C)C2(OC(=O)C=3C=CC=CC=3)C1C1C=C(CO)CC(C(C(C)=C3)=O)(O)C3C1(O)C(C)C2OC(=O)C1=CC=CC=C1 FQHYQCXMFZHLAE-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- GLJFYGFBITUZOE-UHFFFAOYSA-N 4-phenylbutylbenzene Chemical compound C=1C=CC=CC=1CCCCC1=CC=CC=C1 GLJFYGFBITUZOE-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- GEJYBLVERMUSTA-UHFFFAOYSA-K C(CCC)(=O)[O-].[Ir+3].C(CCC)(=O)[O-].C(CCC)(=O)[O-] Chemical compound C(CCC)(=O)[O-].[Ir+3].C(CCC)(=O)[O-].C(CCC)(=O)[O-] GEJYBLVERMUSTA-UHFFFAOYSA-K 0.000 description 1
- HDIJJXDMGPPQGV-UHFFFAOYSA-K C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Ru+3].C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCCCC)(=O)[O-] Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Ru+3].C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCCCC)(=O)[O-] HDIJJXDMGPPQGV-UHFFFAOYSA-K 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004157 Nitrosyl chloride Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910021549 Vanadium(II) chloride Inorganic materials 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- LIABKAQKQSUQJX-UHFFFAOYSA-N [Mn].[Pb] Chemical compound [Mn].[Pb] LIABKAQKQSUQJX-UHFFFAOYSA-N 0.000 description 1
- YPGLWPWPVJBCEM-UHFFFAOYSA-K [Pt+3].[O-]P([O-])([O-])=O Chemical compound [Pt+3].[O-]P([O-])([O-])=O YPGLWPWPVJBCEM-UHFFFAOYSA-K 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- MMCPOSDMTGQNKG-UJZMCJRSSA-N aniline;hydrochloride Chemical compound Cl.N[14C]1=[14CH][14CH]=[14CH][14CH]=[14CH]1 MMCPOSDMTGQNKG-UJZMCJRSSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- XQRVLQLHRAJWLU-UHFFFAOYSA-K antimony(3+);butanoate Chemical compound [Sb+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O XQRVLQLHRAJWLU-UHFFFAOYSA-K 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- WIBSOCZUJHHNDP-UHFFFAOYSA-N cadmium(2+) dioxido(dioxo)manganese Chemical compound [Mn](=O)(=O)([O-])[O-].[Cd+2] WIBSOCZUJHHNDP-UHFFFAOYSA-N 0.000 description 1
- PSIBWKDABMPMJN-UHFFFAOYSA-L cadmium(2+);diperchlorate Chemical compound [Cd+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PSIBWKDABMPMJN-UHFFFAOYSA-L 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001785 cerium compounds Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HOIFCIDJYJBWSD-UHFFFAOYSA-N chloromethylbenzene Chemical compound ClCC1=CC=CC=C1.ClCC1=CC=CC=C1 HOIFCIDJYJBWSD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FXGFZZYDXMUETH-UHFFFAOYSA-L difluoroplatinum Chemical compound F[Pt]F FXGFZZYDXMUETH-UHFFFAOYSA-L 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229940046149 ferrous bromide Drugs 0.000 description 1
- 239000004225 ferrous lactate Substances 0.000 description 1
- 235000013925 ferrous lactate Nutrition 0.000 description 1
- 229940037907 ferrous lactate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- QXZANYPVYZTYBN-UHFFFAOYSA-N heptan-3-ylbenzene Chemical compound CCCCC(CC)C1=CC=CC=C1 QXZANYPVYZTYBN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- VNVQLDDPGAWSSB-UHFFFAOYSA-H iridium(3+);trisulfate Chemical compound [Ir+3].[Ir+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNVQLDDPGAWSSB-UHFFFAOYSA-H 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- BMNDJWSIKZECMH-UHFFFAOYSA-N nitrosyl bromide Chemical compound BrN=O BMNDJWSIKZECMH-UHFFFAOYSA-N 0.000 description 1
- VPCDQGACGWYTMC-UHFFFAOYSA-N nitrosyl chloride Chemical compound ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 description 1
- 235000019392 nitrosyl chloride Nutrition 0.000 description 1
- OSDZHDOKXGSWOD-UHFFFAOYSA-N nitroxyl;hydrochloride Chemical compound Cl.O=N OSDZHDOKXGSWOD-UHFFFAOYSA-N 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- TVAHQEUJLZYCGY-UHFFFAOYSA-N osmium(4+);tetracyanide Chemical compound [Os+4].N#[C-].N#[C-].N#[C-].N#[C-] TVAHQEUJLZYCGY-UHFFFAOYSA-N 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- ZVSLRJWQDNRUDU-UHFFFAOYSA-L palladium(2+);propanoate Chemical compound [Pd+2].CCC([O-])=O.CCC([O-])=O ZVSLRJWQDNRUDU-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- ZZMFAAPZGBNYRP-UHFFFAOYSA-J phosphonato phosphate platinum(4+) Chemical compound [Pt+4].[O-]P([O-])(=O)OP([O-])([O-])=O ZZMFAAPZGBNYRP-UHFFFAOYSA-J 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 description 1
- QRRFFHBDASQYFJ-UHFFFAOYSA-K rhodium(3+);triformate Chemical compound [Rh+3].[O-]C=O.[O-]C=O.[O-]C=O QRRFFHBDASQYFJ-UHFFFAOYSA-K 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- LECPYKYNIWHZFT-UHFFFAOYSA-K ruthenium(3+) triperchlorate Chemical compound [Ru+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LECPYKYNIWHZFT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- ITAKKORXEUJTBC-UHFFFAOYSA-L vanadium(ii) chloride Chemical compound Cl[V]Cl ITAKKORXEUJTBC-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B39/00—Halogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Definitions
- This invention relates to a process for preparing a nuclear chloro or nuclear bromo aromatic hydrocarbon.
- Chlorination or bromination of aromatic hydrocarbons can be effected, for example, by passing gaseous chlorine or bromine therethrough under appropriate reaction conditions. These processes are undesirable, however, for with the production of one mol of the halogenated aromatic hydrocarbon, one mol of undesired, and generally unusable, HCl or HBr is also produced.
- HCl is used to chlorinate benzene, but this oxychlorination involves a vapor phase reaction with oxygen and high temperatures.
- the Raschig process is not satisfactory for aromatics, except for benzene, since they are easily oxidized at the high temperatures, and in all cases conversion levels must be kept low (10 percent or less), because dichlorination becomes appreciable.
- the aromatic hydrocarbon reactant employed herein can be an aromatic hydrocarbon, a halogenated (chloro, bromo, fiuoro, or iod-o) aromatic hydrocarbon, or a carboxylic acid ester of a hydroxyanomatic.
- the carboxylic acid portion can be derived from the group of carboxylic acids, straight and branched chain, having from one to forty, preferably from two to six carbon atoms.
- carboxylic acids examples include the alkanoic acids such as formic, acetic, propionic, butyric, pivalic, octanoic, isooctanoic, benzoic, lauric, stearic, isobutyric, para-toluic, gamma-chlorobutyric, tetracontanoic, phenylacetic, cyclohexane carboxylic, crot-onic, furoic, heptanoic, eicosanoic, etc.
- aromatic hydrocarbons examples include benzene, toluene,
- Also present in the reaction system herein is a substance selected from the group consisting of copper, manganese, cerium, cobalt, vanadium, chromium, iron, nickel, cadmium, tin, antimony, mercury, bismuth, the noble metals and compounds of these metals which are mainly the salts and oxides of these metals.
- Examples of compounds that can be employed herein include metallic iron, ferric acetate, ferric propionate, ferric hydroxy acetate, ferric chloride, ferric hydroxide, ferric nitrate, ferric phosphate, ferric sulfate, ferrous acetate, ferrous nitrate, ferrous lactate, ferrous bromide, palladium, rhodium, iridium, osmium, ruthenium, platinum, rhodium formate, palladium acetate, palladium propionate, iridium butyrate, palladium pivalate, palladium octanoate, osmium isooctanoate, palladium benzoate, palladium laurate, ruthenium stearate, palladium isobutyrate, palladium para-toluate, platinum gamma-chlorobutyrate, ruthenium tetracontanoate, osmium phenyla
- the cationic portion of the salt can be one of the defined noble metals, palladium, while the anionic portion thereof can be derived from the group of carboxylic acids, straight and branched chain, having from one to forty carbon atoms, preferably from two to six carbon atoms, examples of which have been identified above.
- nitrate ions I mean to include NO a singly charged anion containing one nitrogen atom and three oxygen atoms.
- nitrite ion I mean to include N0 a singly charged anion containing one nitrogen atom and two oxygen atoms.
- Examples of compounds that can be employed include nitric acid, sodium nitrate, cesium nitrate, sodium nitrite, potassium nitrite, nitric oxide, nitrous anhydride, nitrous acid, nitrogen dioxide, nitrogen tetroxide, nitric anhydride, nitrosyl chloride, nitrosyl bromide, nitroxyl chloride, etc. Additionally there 3 must be present in the reaction system chloride ions or bromide ions in suflicient quantities to halogenate the aromatic compound defined above.
- chloride ions or bromide ions I mean a singly negatively charged chlorine or bromine atom.
- the chloride ion or bromide ion can be obtained from one of the metal compounds defined hereinabove, such as ferric chloride or palladium chloride, this is not preferred.
- the chloride ion or bromide ion is obtained from any compound which is capable of dissociating in the reaction system to chloride or bromide ions, such as hydrogen chloride, hydrogen bromide, ammonium chloride, ammonium bromide, organic chlorides and bromides such as aniline hydrochloride, methyl amine hydrochloride, benzyl trimethyl ammonium bromide and metallic chlorides and bromides such as sodium chloride, potassium bromide, rubidium chloride, magnesium bromide, cupric chloride, barium chloride, calcium chloride, aluminum bromide, etc.
- the amount of chloride or bromide ion present in the system relative to the aromatic hydrocarbon reactant on a molar basis can be from about 10:1 to about 1:20, preferably from about 2:1 to about 1:2.
- the reaction defined herein in a preferred embodiment, is carried out in the presence of molecular oxygen.
- molecular oxygen When this is done, less nitrate ion, nitrite ion, NO or N is required, less iron or noble metal or salt thereof is needed and the process can be carried out in a continuous manner.
- the amount of molecular oxygen that can be employed relative to the aromatic hydrocarbon reactant, on a molar basis, can be from about 1000:1 to about 1:10, preferably from about :1 to about 1:1.
- the reactants employed herein are heated together in an inert organic solvent which will not adversely affect preferably from about 0.01 percent to about one percent.
- the amount of nitrate ion, nitrite ion, NO or'NO employed, on a molar basis, relative to the aromatic compound can be from about 1:1 to about 1:10 preferably from about 1:3 to about 1:10".
- the amount of solvent employed can be from about 0.1 to about 1000 mols, preferably from about one to about fifty mols, per mol of aromatic compound.
- the temperature employed during the process can range from about 15 to about 200 0, preferably from about 60 to about 150 C., the pressure from about 0.1 to about 10,000 pounds per square inch gauge, preferably from about ten to about 1000 pounds per square inch gauge and the contact time from about 0.0001 to about 200, preferably from about one to about ten hours.
- the desired chloro or bromo aromatic compound can be recovered from the reaction mixture in any suitable manner, for example, by distillation at a temperature of about to about 200C. and a pressure of about 0.001 to about ten pounds per square inch gauge. Depending upon the boiling points of the products in the reaction mixture, the individual components thereof, including the desired chloro or bromo aromatic, will come off individually overhead and can thus be easily recovered.
- the solvent is a liquid carboxylic TABLE II Millimols 0f- Reac- Pallation Milli, drum Acetic time, niols Salt acetate Benzene HNOa NaNOg HCl acid hours product Product 10 0 1. O 20. 0 5. 0. 0. O 400 66 0. O3 Phcnyl acetate.
- the reaction defined herein is simply effected by bringing the materials together into contact with each other under specified conditions.
- the amount of metal, or compounds thereof, as metal, on a molar basis, employed can A series of runs were carried out wherein a mixture of reactants was refluxed at atmospheric pressure and 115 C. Analysis of the reaction product by gas chromatography resulted in the following data which illustrate range from about 0.0001 percent to about five percent, that noble metals are effective herein.
- EXAMPLE 1V EXAMPLE VI An additional series of runs were carried out wherein A mixture of 0.2282 gram of palladium acetate, 0.6298 various aromatic compounds, palladium acetate, NaCl, grams of sodmm chloride, 0.7405 gram of sodium nitrite, HNO and acetic acid were refluxed at atmospheric pres- 35 1.83 grams of benzene and milliliters of acetic acid sure and a temperature of 116 C. The results are tabuwas refluxed for 20 hours at atmospheric pressure and a lated below in Table IV. temperature of 11 C. Analysis by gas chromatography TABLE IV Millimols of Reac- Millition mols of Aromatic Palladium time, acetlc Run No.
- EXAMPLE V showed the presence of 4.1 millimols of chlorobenzene.
- the stirred mixture had a pres- 60 acld were heated at 100 under all Oxygen Pressure sure of 26 pounds per square inch gauge.
- the pressure of P0111111s P q f Inch gauge for five hOIlrS- Gas was brought up to 60 pounds total with oxygen and rechrqmatographlc analysls Showed the p fi f 0f elghty pressured to this pressure with oxygen when the total presmllllmols 0f ortho chlofotolPfifne, 1111111111015 of p Sure fell below 40 pounds square i gauge d i a chlorotoluene and 1.35 mllhmols of d1chlorotoluene.
- matic ring contains at least one hydrogen, such as toluene, chlorotoluene is first formed and if reaction is continued the chlorotoluene is converted to chlorobenzoic acid. This is illustrated in the following runs at C. and
- the following series of experiments show the wide variety of metal compounds that can be used in the catalyst system in oxychlorination. Each run was made at 3() 120 C. and under 170 pounds per square inch gauge of oxygen for four hours. The wellstirred charge contained millimols of HCl, 10 millimols of HNO 1990 millimols of acetic acid, and 303 millimols of toluene was used in each case. In these runs oxygen is maintained at 170 pounds per square inch gauge in the reactor but is fed from a bomb where the drop in pressure is noted.
- EXAMPLE XII I expected that oxychlorination could be hastened with palladium or copper used in addition to a side chain oxidation catalyst. Thus, the palladium or copper would accelerate the formation of chlorotoluene and the cobalt, manganese, cerium or vanadium compound would catalyze the further oxidation to chlorobenzoic acid. Unexpectedly it was found that copper and palladium inhibit and prevent the subsequent methyl group oxidation.
- a process for preparing a halogenated aromatic hydrocarbon selected from the .group consisting of chloro and bromo aromatic hydrocarbons which consists of heating an aromatic compound selected from the group consisting of an aromatic hydrocarbon and a halogenated aromatic hydrocarbon with (1) a metal selected from the group consisting of platinum, palladium, iridium, rhodium, osmium, ruthenium, copper, manganese, cerium, cobalt, vanadium, chromium, iron, nickel, cadmium, tin, antimony, mercury and bismuth or salts or oxides of these metals, (2) a substance selected from the group consisting of nitrate ions, nitrite ions, NO and N0 and (3) a halogen ion selected from the group consisting of chloride ions and bromide ions in an inert organic solvent, wherein the reaction is carried out at a temperature of about to about 200 C.
- a pressure of about 0.1 to about 10,000 pounds per square inch gauge for about 0.0001 to about 200 hours with the amount of halogen relative to the aromatic hydrocarbon, on a molar basis, being from about 10:1 to about 1:20, the amount of metal or salt or oxide thereof, on a molar basis, being from about 0.0001 to about five percent, and the amount of nitrate, nitrite, NO or N0 on a molar basis, relative to the aromatic hydrocarbon being from about 1:1 to about 1210*.
- said salt is an alkanoic carboxylic acid salt of platinum, palladium, iridium, rhodium, osmium or ruthenium.
- the process of claim 1 are obtained from NaCl.
- metal is iridwherein said chloride ions chloride ions 34.
- said metal is selected from the group consisting of cobalt, cerium, vanadium and manganese and said aromatic hydrocarbon compound carries from one to five alkyl substituents wherein the carbon adjacent to the aromatic hydrocarbon ring contains at least one hydrogen.
Abstract
A PROCESS FOR PREPARING A NUCLEAR CHLORO OR NUCLEAR BROMO AROMATIC HYDROCARBON WHICH INVOLVES HEATING AN AROMATIC COMPOUND WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF COPPER, MANGANESE, CERIUM, COBALT, VANADIUM, CHROMIUM, IRON, NICKEL, CADMIUM,TIN, ANTIMONY, MERCURY, BISMUTH, THE NOBLE METALS (PLATINUM, PALADIUM IRIDIUM, RHODIUM, OSMIUM AND RUTHENIUM) AND COMPOUNDS OF THESE METALS, A NITRATE ION, A NITRITE ION, NO OR NO2, A CHLORIDE OR BROMIDE ION AND AN INERT SOLVENT.
Description
United States Patent 3,591,645 PROCESS FOR PREPARING A HALOGENATED AROMATIC Charles M. Selwitz, Pitcairn, Pa., assiguor to Gulf Research & Development Company, Pittsburgh, Pa. No Drawing. Continuation-impart of application Ser. No. 602,469, Dec. 19, 1966. This application May 20, 1968, Ser. No. 730,589
Int. Cl. C07c /04 US. Cl. 260-'650 38 Claims ABSTRACT OF THE DISCLOSURE A process for preparing a nuclear chloro or nuclear bromo aromatic hydrocarbon which involves heating an aromatic compound with a compound selected from the group consisting of copper, manganese, cerium, cobalt, vanadium, chromium, iron, nickel, cadmium, tin, antimony, mercury, bismuth, the noble metals (platinum, palladium, iridium, rhodium, osmium and ruthenium) and compounds of these metals, a nitrate ion, a nitrite ion, NO or N0 a chloride or bromide ion and an inert solvent.
This application is a coutinuation-in-part application of my application Ser. No. 602,469 filed Dec. 19, 1966, now abandoned.
This invention relates to a process for preparing a nuclear chloro or nuclear bromo aromatic hydrocarbon.
Chlorination or bromination of aromatic hydrocarbons can be effected, for example, by passing gaseous chlorine or bromine therethrough under appropriate reaction conditions. These processes are undesirable, however, for with the production of one mol of the halogenated aromatic hydrocarbon, one mol of undesired, and generally unusable, HCl or HBr is also produced. In the Raschig process, a technique has been developed whereby HCl is used to chlorinate benzene, but this oxychlorination involves a vapor phase reaction with oxygen and high temperatures. The Raschig process is not satisfactory for aromatics, except for benzene, since they are easily oxidized at the high temperatures, and in all cases conversion levels must be kept low (10 percent or less), because dichlorination becomes appreciable.
I have found that nuclear chlorination or bromination of an aromatic hydrocarbon can easily be effected, without resorting to vapor phase reactions, and good conversions and high yields to desired product can be attained, by heating said aromatic hydrocarbon in the presence of a compound selected from the group consisting of copper, manganese, cerium, cobalt, vanadium, chromium, iron, nickel, cadmium, tin, antimony, mercury, bismuth, the noble metals (platinum, palladium, iridium, rhodium, osmium and ruthenium) and compounds of these metals, a substance selected from the group consisting of nitrate ions, nitrite ions, NO and N0 21 chloride or bromide ion and an inert organic solvent.
The aromatic hydrocarbon reactant employed herein can be an aromatic hydrocarbon, a halogenated (chloro, bromo, fiuoro, or iod-o) aromatic hydrocarbon, or a carboxylic acid ester of a hydroxyanomatic. The carboxylic acid portion can be derived from the group of carboxylic acids, straight and branched chain, having from one to forty, preferably from two to six carbon atoms. Examples of such carboxylic acids are the alkanoic acids such as formic, acetic, propionic, butyric, pivalic, octanoic, isooctanoic, benzoic, lauric, stearic, isobutyric, para-toluic, gamma-chlorobutyric, tetracontanoic, phenylacetic, cyclohexane carboxylic, crot-onic, furoic, heptanoic, eicosanoic, etc. Examples of such aromatic hydrocarbons that can be employed herein include benzene, toluene,
3,591,645 Patented July 6, 1971 ethylbenzene, cumene, naphthalene, anthracene, biphenyl, phenanthrene, t-butylbenzene, a-phenyluaphthalene, paraxylene, polystyrene, terphenyl, 3-phenylheptane, 1,4-diphenyl butane, diphenyl methane, tetralin, propylium anion, etc.
Also present in the reaction system herein is a substance selected from the group consisting of copper, manganese, cerium, cobalt, vanadium, chromium, iron, nickel, cadmium, tin, antimony, mercury, bismuth, the noble metals and compounds of these metals which are mainly the salts and oxides of these metals. Examples of compounds that can be employed herein include metallic iron, ferric acetate, ferric propionate, ferric hydroxy acetate, ferric chloride, ferric hydroxide, ferric nitrate, ferric phosphate, ferric sulfate, ferrous acetate, ferrous nitrate, ferrous lactate, ferrous bromide, palladium, rhodium, iridium, osmium, ruthenium, platinum, rhodium formate, palladium acetate, palladium propionate, iridium butyrate, palladium pivalate, palladium octanoate, osmium isooctanoate, palladium benzoate, palladium laurate, ruthenium stearate, palladium isobutyrate, palladium para-toluate, platinum gamma-chlorobutyrate, ruthenium tetracontanoate, osmium phenylacetate, iridium cyclohexane carboxylate, rhodium crotonate, palladium furoate, palladium heptanoate, palladium eicosano'ate, palladium chloride, palladium nitrate, palladium oxide, rhodium bromide, iridium sulfate, osmium cyanide, ruthenium perchlorate, rhodium iodide, platinum fluoride, platinum phosphate, platinum pyrophosphate, ruthenium oxide, pl'atinic bromide, platinous bromide, platinum oxide, platinous cyanide, platinum hydroxide, rhodium sulfate, rhodium oxide, osmium tetroxide, ruthenium trichloride, iridium oxide, metallic copper, cupric nitrate, cuprous chloride, cupric acetate, manganese, manganic oxide, manganese acetate, cerium, cerous nitrate, ceric ammonium sulfate, cobalt, cobaltous bromide, cobaltous fluoride, cobaltous perchlorate, cobaltic chloride, vanadium, vanadium pentoxide, vanadium dichloride, vanadium pentafiuoride, vanadyl bromide, chromium, chromium trioxide, chromic acetate, nickel, nickel acetate, nickel nitrate, cadmium, cadmium perchlorate, cadmium manganate, tin, tin tetrachloride, tin trifiuoride, tin sulfate, antimony, antimony chloride, antimony butyrate, mercury, mercuric acetate, mercuric nitrate, bismuth, bismuth phosphate, bismuth arsenate, bismuth oxychloride, etc.
Of the noble metal compounds that are employed herein, I prefer a carboxylic acid salt of a noble metal. Thus, the cationic portion of the salt can be one of the defined noble metals, palladium, while the anionic portion thereof can be derived from the group of carboxylic acids, straight and branched chain, having from one to forty carbon atoms, preferably from two to six carbon atoms, examples of which have been identified above.
In order to obtain the desired conversion herein it is imperative that the above materials be brought into contact with each other in the presence of a substance selected from the group consisting of nitrate ions, nitrite ions, NO and N0 Thus, any compound falling within the above definition or which, for example, by ionization, oxidation or disproportionation, under the reaction conditions defined herein will result in the same can be employed. By nitrate ions I mean to include NO a singly charged anion containing one nitrogen atom and three oxygen atoms. By nitrite ion I mean to include N0 a singly charged anion containing one nitrogen atom and two oxygen atoms. Examples of compounds that can be employed include nitric acid, sodium nitrate, cesium nitrate, sodium nitrite, potassium nitrite, nitric oxide, nitrous anhydride, nitrous acid, nitrogen dioxide, nitrogen tetroxide, nitric anhydride, nitrosyl chloride, nitrosyl bromide, nitroxyl chloride, etc. Additionally there 3 must be present in the reaction system chloride ions or bromide ions in suflicient quantities to halogenate the aromatic compound defined above. By chloride ions or bromide ions I mean a singly negatively charged chlorine or bromine atom. Although the chloride ion or bromide ion can be obtained from one of the metal compounds defined hereinabove, such as ferric chloride or palladium chloride, this is not preferred. Desirably the chloride ion or bromide ion is obtained from any compound which is capable of dissociating in the reaction system to chloride or bromide ions, such as hydrogen chloride, hydrogen bromide, ammonium chloride, ammonium bromide, organic chlorides and bromides such as aniline hydrochloride, methyl amine hydrochloride, benzyl trimethyl ammonium bromide and metallic chlorides and bromides such as sodium chloride, potassium bromide, rubidium chloride, magnesium bromide, cupric chloride, barium chloride, calcium chloride, aluminum bromide, etc. The amount of chloride or bromide ion present in the system relative to the aromatic hydrocarbon reactant on a molar basis can be from about 10:1 to about 1:20, preferably from about 2:1 to about 1:2.
The reaction defined herein, in a preferred embodiment, is carried out in the presence of molecular oxygen. When this is done, less nitrate ion, nitrite ion, NO or N is required, less iron or noble metal or salt thereof is needed and the process can be carried out in a continuous manner. The amount of molecular oxygen that can be employed relative to the aromatic hydrocarbon reactant, on a molar basis, can be from about 1000:1 to about 1:10, preferably from about :1 to about 1:1.
The reactants employed herein are heated together in an inert organic solvent which will not adversely affect preferably from about 0.01 percent to about one percent. The amount of nitrate ion, nitrite ion, NO or'NO employed, on a molar basis, relative to the aromatic compound, can be from about 1:1 to about 1:10 preferably from about 1:3 to about 1:10". The amount of solvent employed can be from about 0.1 to about 1000 mols, preferably from about one to about fifty mols, per mol of aromatic compound. The temperature employed during the process can range from about 15 to about 200 0, preferably from about 60 to about 150 C., the pressure from about 0.1 to about 10,000 pounds per square inch gauge, preferably from about ten to about 1000 pounds per square inch gauge and the contact time from about 0.0001 to about 200, preferably from about one to about ten hours.
At the end of the reaction period, the desired chloro or bromo aromatic compound can be recovered from the reaction mixture in any suitable manner, for example, by distillation at a temperature of about to about 200C. and a pressure of about 0.001 to about ten pounds per square inch gauge. Depending upon the boiling points of the products in the reaction mixture, the individual components thereof, including the desired chloro or bromo aromatic, will come off individually overhead and can thus be easily recovered.
The process of the invention can further be illustrated by the following.
EXAMPLE I A mixture of reactants, as set forth below in Table I, was refluxed at atmospheric pressure and 115 C. Analysis by gas chromatography resulted in data reproduced below in Table I.
TABLE I Millimols 0f Reaction Milli- Milli- Palladium Acetic time, mols mols Salt acetate Benzene IINOJ acid hours NaNOa Product product 10. 0 1. 0 20. 0 5. 0 400 66 0. 03 10.0 1.0 20.0 5.0 400 66 O. 93 10. 0 1. O 20. 0 5. 0 400 6G 4. 1 10. 0 1.0 20. 0 5.0 400 66 2. 8 10. 0 1.0 20.0 5.0 400 66 0.0 10. 0 1.0 20. 0 5.0 400 66 0.0 10. 0 1. 0 20. 0 l5. 0 400 2 1 0. 0 l0. 0 1. 0 20. 0 10. 0 400 24 0. 0 5. 1 1. 0 160. 0 0. O 400 24 0. 0 5. 6 1. 0 20. 0 0.0 400 24 O. 0 5. 1 1.0 160.0 5.0 400 24 0. 0 5. 6 1.0 20. 0 5. 0 400 24 0. 0 10.0 1.1 20.0 0.0 400 24 7. 2
the course of the reaction and will not react with the 50 reactants and/or the products produced herein. Examples of such solvents are ethers, amides, sulfoxides, ketones, such as meta dioxane, dimethylacetamide, dimethylformamide, dimethylsulfoxide, acetone, etc. In a preferred EXAMPLE II A mixture of reactants, as set forth below in Table II, was refluxed at atmospheric pressure and 115 C. Analysis by gas chromatography resulted in the following data.
embodiment, however, the solvent is a liquid carboxylic TABLE II Millimols 0f- Reac- Pallation Milli, drum Acetic time, niols Salt acetate Benzene HNOa NaNOg HCl acid hours product Product 10 0 1. O 20. 0 5. 0. 0. O 400 66 0. O3 Phcnyl acetate.
0. 0 5. 0 20. 0 10. 0 0. 0 0. 0 400 24 3. 3 Do. 10. 0 1. 0 20. 0 5. 0 O. 0 0. 0 400 6G 4. 1 CuHsCl 10. 0 1. 1 20. 0 0. O 11. 0 0. 0 400 24 7. 2 CuHsCl 0 0 1. 2 20. 0 0. 0 0. 0 l2. 0 400 24 0. 0 None.
acid, straight or branched chain, having preferably from one to ten carbon atoms, more preferably from two to six carbon atoms, specific examples of which have been set forth above.
The reaction defined herein is simply effected by bringing the materials together into contact with each other under specified conditions. The amount of metal, or compounds thereof, as metal, on a molar basis, employed can A series of runs were carried out wherein a mixture of reactants was refluxed at atmospheric pressure and 115 C. Analysis of the reaction product by gas chromatography resulted in the following data which illustrate range from about 0.0001 percent to about five percent, that noble metals are effective herein.
TABLE III Reac- Milli- Gram Milli- Millimols of tion mols Milliatoms of mOls time, acetic mols Metal metal HNO; Salt Salt Benzene NaNOa H01 hours acid Product product 0.13 1.0 N201 10.0 20.0 0.0 0.0 03 400 0611501 2.6 0.10 1.0 N201 10.0 20.0 0.0 0.0 93 400 0611501 0.45 0. 25 1.0 N201 10.0 20.0 0.0 0.0 93 400 0611 01 0.12 0.13 1.0 N201 10.0 20.0 0.0 0.0 93 400 06H501 0. 09 0.24 1.0 NaCl 10.0 20.0 0.0 0.0 93 400 0111501 0.01 0.28 1.0 NaBr 10.0 20.0 0.0 0.0 03 400 CBH B1' 0. 03 0.12 10.0 NaBi 11.0 20.0 0.0 0.0 17.5 400 01mm 0.17 o. 13 10.0 NaCl 10.0 20.0 0.0 0.0 17.5 400 0611501 2.3 0.13 10.0 N201 10.0 20.0 0.0 0.0 17.5 400 061-1 01 2.9 0.11 10.0 NaOl 10.0 20.0 0.0 0.0 17.5 400 0611501 4.2 0. 23 10.0 NaCl 10.0 20.0 0.0 0.0 17.5 400 0111501 2.5 0.15 10.0 N201 10.0 20.0 0.0 0.0 17.5 400 0511501 2.9 0.12 10.0 NaBr 11.0 20.0 0.0 0.0 24 400 C6H5Bl' 0.67 0.13 10.0 NaCl 10.0 20.0 0.0 0.0 24 400 0511501 2.3 0.13 10.0 NaOl 10.0 20.0 0.0 0.0 24 400 0511501 3.3 0.11 10.0 N201 10.0 20.0 0.0 0.0 24 400 0.11 01 4.2 0. 23 10.0 NaCl 10.0 20.0 0.0 0.0 24 400 0411501 3.0 0.15 10.0 NaCl 10.0 20.0 0.0 0.0 24 400 001501 4.5 0.12 15.0 N231 11.0 20.0 0.0 0.0 15 400 01.11am 0.78 0.13 15.0 N201 10.0 20.0 0.0 0.0 15 400 0.11501 4.1 0.13 15.0 N201 10.0 20.0 0.0 0.0 15 400 0111501 4.2 0.11 15.0 N201 10.0 20.0 0.0 0.0 15 400 0.11501 5.0 0.23 15.0 NaCl 10.0 20.0 0.0 0.0 16 400 011 1501 4.0 0.13 15.0 N201 10.0 20.0 0.0 0.0 15 400 0511 01 0.1 0.12 15.0 NaBr 11.0 20.0 0.0 0.0 20 400 05mm 0.80 0.13 15.0 NaCl 10.0 20.0 0.0 0.0 20 400 06H501 4.2 0.13 15.0 N201 10.0 20.0 0.0 0.0 20 400 C5H Cl 4.2 0.11 15.0 N201 10.0 20.0 0.0 0.0 20 400 C5H Ol 5.5 0.23 15.0 N201 10.0 20.0 0.0 0.0 20 400 0111501 4.2 0.16 15.0 NaCl 10.0 20.0 0.0 0.0 20 400 0511601 5.1 0.14 0.0 N201 10.0 20.0 11.0 0.0 24 400 0611,01 2.1 0.12 0.0 None 0.0 20.0 0.0 12.0 24 400 None 0.0 0. 03 1.0 N201 11.0 20.0 0.0 0.0 19 400 0111501 Trace 0.03 6.0 N201 11.0 20.0 0.0 0.0 17 400 0111501 0.45
EXAMPLE 1V EXAMPLE VI An additional series of runs were carried out wherein A mixture of 0.2282 gram of palladium acetate, 0.6298 various aromatic compounds, palladium acetate, NaCl, grams of sodmm chloride, 0.7405 gram of sodium nitrite, HNO and acetic acid were refluxed at atmospheric pres- 35 1.83 grams of benzene and milliliters of acetic acid sure and a temperature of 116 C. The results are tabuwas refluxed for 20 hours at atmospheric pressure and a lated below in Table IV. temperature of 11 C. Analysis by gas chromatography TABLE IV Millimols of Reac- Millition mols of Aromatic Palladium time, acetlc Run No. Aromatic compound compound acetate NaOl HNOa hours acld Product and millimols of product 53 Phenyl acetate 20.0 1.0 13.0 10.0 21 400 p-Chlorophenol (0.04), p-chlorophenyl acetate (0.01) and o-chlorophenyl acetate. 54 To uene 0.0 1.2 12.0 10.0 21 400 o-Chlorotoluene (0.9) and mand pehlorotoluene (4.5) 55 Anisole 20.0 1.0 9.0 10.0 21 400 Small amounts of a numb f V p pounds,not identified. 56- -.l Chlorobenzene 20.0 1.0 10.0 10.0 21 400 o-Dichlorobenzene (O) m.di hl r Regrgene (0.22) and p-dichlorobenzenc 57 Methyl 1221120213-.-- 20.0 1.0 11.0 10.0 21 400 Small amounts of a number of pounds, not identified. 5B Acetophenone 20.0 1.0 10.0 10.0 21 400 N0 reaction. 59 Naphthalene 20.0 1.1 10.0 10.0 21 400 2-chl0r0naphthalene (0,47) and 1- 1 chloronaphthalene (0,7).
EXAMPLE V showed the presence of 4.1 millimols of chlorobenzene.
A mixture of 3.9 grams of hydrogen chloride, 2.0 mil- EXAMPLE VII liliters of percent aqueous nitric acid, 15.4 grams of benzene, grams of acetic acid and 1.77 grams of pal- InlXture 0f m111 11T 11$ 0f Palladlum a 252 ladium chloride was placed into a 200-milliliter high 111111131018 of 310 0 1 1 of toluene, 10 ITlllllIIlOlS pressure glass bomb which ,1 contained a magnetic of 70 percent aqueous nitric acid and 159 grams of acetic v 0 stirrer and a thermowell. The stirred mixture had a pres- 60 acld were heated at 100 under all Oxygen Pressure sure of 26 pounds per square inch gauge. The pressure of P0111111s P q f Inch gauge for five hOIlrS- Gas was brought up to 60 pounds total with oxygen and rechrqmatographlc analysls Showed the p fi f 0f elghty pressured to this pressure with oxygen when the total presmllllmols 0f ortho chlofotolPfifne, 1111111111015 of p Sure fell below 40 pounds square i gauge d i a chlorotoluene and 1.35 mllhmols of d1chlorotoluene. two-hour period. Total oxygen consumption was 90 5 Thus, there are formed 113 H1013 of Product PQ 11101 pounds The increase in Weight of the product was 39 palladlurn and 24 mols of product per mol of n1tr1c acid. grams and there was found, by gas chromatography, 8.8 EXAMPLE VIII grams of chlorobenzene, 0.12 gram of ortho dichlorobenzene and 0,19 gram of para dichlorobenzene. The oxygen In the following series of reactions with toluene at enables far more product to form than can be accounted 70 120 C. under pounds per square inch gauge of oxyfor by the palladium salt or the nitr1c acid. Thus, thls gen for four hours it can be seen that little or no reillustrates a truly catalytic reaction action occurred in runs where either inert solvent, or
Pd catalyst, or both, were missing, but in runs with both, exgl M01 H20 cellent conversion of reactants to chlorotoluene was ob- 75 tained.
TAB LE V Millimoles Conversion Acetic Conversion based on Run No Catalyst Catalyst HCl HNOa Water acid Toluene based on 1101 toluene o 68.5 2. 4 0 1, 473 0 0 2 46. 6 2. 4 0 0 1, 473 0 0 0 183. 5 9. 6 0 1, 990 303 6. 5 3. 9 10 175. 5 9. 6 0 l, 990 303 75. 0 43. 4 2 252 10. 3 0 2, 650 310 93. 0 75. 8 69 CL1(OAO)2 10 268 11. 1 1,928 1,990 303 91.4 80.9 Cu(OAc)z 10 65. 8 2. 4 0 0 1, 522 0 0 71 C11(0AC)2 10 26. 8 11. l 945 1, 990 303 95. 6 84. 7
*OAc=Acetate.
EXAMPLE IX alkyl substituents wherein the carbon adjacent to the aro- The necessity of both inert solvent and catalyst is again demonstrated in the following series of runs with mesitylone run at 70 C. and pounds per square inch gauge of oxygen for four hours.
matic ring contains at least one hydrogen, such as toluene, chlorotoluene is first formed and if reaction is continued the chlorotoluene is converted to chlorobenzoic acid. This is illustrated in the following runs at C. and
TABLE VI Millirnols Acetic Reaction Run N0 Catalyst HCl HNOa Water acid Mcsitylcne occurring 7?. Pd(OAc)g.- 26. 8 11. 1 945 1, 990 303 Yes.
None 57.5 2.4 None None 1,155 No. 74 Pd(OAc)g 55.0 2.4 None None 1,155 No.
EXAMPLE X pounds per square inch gauge of oxygen in which 270 The following series of experiments show the wide variety of metal compounds that can be used in the catalyst system in oxychlorination. Each run was made at 3() 120 C. and under 170 pounds per square inch gauge of oxygen for four hours. The wellstirred charge contained millimols of HCl, 10 millimols of HNO 1990 millimols of acetic acid, and 303 millimols of toluene was used in each case. In these runs oxygen is maintained at 170 pounds per square inch gauge in the reactor but is fed from a bomb where the drop in pressure is noted. For complete conversion to chlorotoluenes a 600 pound drop TABLE VIII Milli- Percent mols Milli- Oxygen 1101 as catamols pressure chloro- Run N0. Catalyst lyst water drop toluene Comments 92 MnO 10 0 ,895 5.5 grams of solids were isolated by filtration. Infrared comparison with authentic samples showed this to be a mixture of para chlorobenzoic acid and orthochlorobenzoic acid with little, if any, benzolc acid. M1102 10 928 788 SOlidsisolated.
8081 02(8) 1, ni. glfilorobgnzoickacid solids isoltted. d d
0 2 roma o ra ic ana sis in icate r0 ucts from t l r V205 10 O 667 42 D g p y p me by 1; cup oxidation V 0 10 928 658 58 D0. c (N0 10 0 1, 000 7. 89 In Runs 98 and 99 nitric acid was not added, the nitrate ion came from the C (N0 10 928 612 97.4 cerium nitrate. In 99 reaction carried only to chlorotoluenes but in 98 ten millimols of metallic compound, 268 millimols of HCl, 303 millimols of toluene, 11.1 millimols of nitric acid, 1990 millimols of acetic acid and 928 millimols of water in each case. The following results were obtained. TAB LE VII Percent con- Percent con- Metal or version of version of metallic HCl to toluene to Run No compound chlorotoluene chlorotoluene 75 Pd 1 97.7 86.5 76.. PM 83.3 29.5 77-- V205 39. 7 35. 1 7 CrClz 35. 1 31.1 79.. FeCla 26. 6 23. 5 80.. Ni(OA0)z 41. 4 36. 4 81.. CdClz 31. 1 27. 5 82.- Sn(Ol)4 28. 4 25. 2 83.- SbClg 41. 2 36. 4 84-- OSCls 41. 4 36. 6 85-. PtClz 29. 2 25. 9 86. HgClz 35. 8 31. 6 87. BiCla 27. 6 27. 1 S8. RhCIs 34. 3 30. 3 89. MnOg 60. 5 53. 5 90. 01101 99. 5 94. 6 91 IdCl 100.0 89. 9
1 Metal.
A1C13, caclz, T1014, ZHCIZ Laclz, Whfin similarly employed showed no catalytic effect.
EXAMPLE XI It has been found that compounds of four metals, cobalt, cerium, vanadium and manganese lead to methyl group oxidation subsequent to oxychlorination, i.e., when the aromatic is a compound carrying from one to five these reacted further to give larger pressure drop and less chlorotoluenes.
EXAMPLE XII I expected that oxychlorination could be hastened with palladium or copper used in addition to a side chain oxidation catalyst. Thus, the palladium or copper would accelerate the formation of chlorotoluene and the cobalt, manganese, cerium or vanadium compound would catalyze the further oxidation to chlorobenzoic acid. Unexpectedly it was found that copper and palladium inhibit and prevent the subsequent methyl group oxidation. This is shown in the following experiments at 170 pounds per square inch gauge of oxygen, with 11.1 millimols of nitric acid, 269 millimols of HCl, 1990 millimols of acetic acid, 928.0 millimols of water and 303 millimols of toluene. Manganese oxide would be expected to bring the total pressure drop to 1788 pounds (Run No. 103) but the addition of palladium or copper acetates limits the pressure drop to about that expected for oxychlorination.
Thus, when palladium or copper compounds are added to systems catalyzed by cobalt, manganese, vanadium or cerium compounds side chain oxidation is inhibited.
EXAMPLE XIII An additional series of runs were made wherein 2.0 millimols of palladium acetate, 269 millimols of HCl, 1990 millimols of acetic acid, 928 millimols of water and 303 millimols of toluene were heated with a nitrogen oxide at 120 C. under 170pounds per square inch gauge of oxygen over a period of four hours. The results obtained are tabulated below in Table X.
TABLE X Oxygen Percent con Millimols pressure version to Nitrogen of nitrodrop in chlorotoluene Run No oxide gen oxide p.s.i.g. based on H01 Note that whereas NO and N0 are convertible to nitrate ions and are operative herein, N 0 is not convertible to nitrate ions and accordingly is inoperative.
Obviously, many modifications and variations of the invention, as hereinabove set forth, can be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.
I claim:
1. A process for preparing a halogenated aromatic hydrocarbon selected from the .group consisting of chloro and bromo aromatic hydrocarbons which consists of heating an aromatic compound selected from the group consisting of an aromatic hydrocarbon and a halogenated aromatic hydrocarbon with (1) a metal selected from the group consisting of platinum, palladium, iridium, rhodium, osmium, ruthenium, copper, manganese, cerium, cobalt, vanadium, chromium, iron, nickel, cadmium, tin, antimony, mercury and bismuth or salts or oxides of these metals, (2) a substance selected from the group consisting of nitrate ions, nitrite ions, NO and N0 and (3) a halogen ion selected from the group consisting of chloride ions and bromide ions in an inert organic solvent, wherein the reaction is carried out at a temperature of about to about 200 C. and a pressure of about 0.1 to about 10,000 pounds per square inch gauge for about 0.0001 to about 200 hours, with the amount of halogen relative to the aromatic hydrocarbon, on a molar basis, being from about 10:1 to about 1:20, the amount of metal or salt or oxide thereof, on a molar basis, being from about 0.0001 to about five percent, and the amount of nitrate, nitrite, NO or N0 on a molar basis, relative to the aromatic hydrocarbon being from about 1:1 to about 1210*.
2. The process of claim 1 wherein said aromatic hydrocarbon compound is benzene.
3. The process of claim 1 wherein said aromatic hydrocarbon compound is toluene.
4. The process of claim 1 wherein said aromatic hydrocarbon compound is chlorobenzene.
5. The process of claim 1 wherein said aromatic hydrocarbon compound is naphthalene.
6. The process of claim 1 wherein said metal is palladium.
7. The process of claim 1 wherein said metal is copper.
8. The process of claim 1 wherein said metal is ruthenium.
9. The process of claim 1 wherein said metal is rhodium.
i 10. The process of claim 1 wherein said mm.
11. The process of claim 1 wherein said salt is a noble metal salt.
12. The process of claim 1 wherein said salt is an alkanoic carboxylic acid salt of platinum, palladium, iridium, rhodium, osmium or ruthenium.
13. The process of claim 1 wherein said salt is palladium acetate. 2
14. The process of claim 1 wherein said salt is cupric acetate. 1 I
15. The process of claim 1 are obtained from NaCl.
16. The process of claim 1 wherein said are obtained from HCl. I
17. The process of claim 1 wherein said bromide ions are obtained from NaBr.
. 18. The process of claim 1 wherein said nitrate ions are obtained from HNO 19. The process of claim 1 wherein said nitrate ions are obtained from NaNO N30. The process of claim 1 wherein said substance is 21. The process of claim 1 wherein said substance is NO.
22. The process of claim 1 wherein said nitrite ions are obtained from sodium nitrite.
23. The process of claim 1 wherein the reaction is carried out in an alkanoic carboxylic acid having from one to ten carbon atoms.
24. The process of claim 1 wherein the reaction is carried out in acetic acid.
25. The process of claim 1 wherein the reaction is carried out in the presence of molecular oxygen.
26. The process of claim 1 wherein a metal salt or oxide of palladium is used, said aromatic hydrocarbon compound is benzene and said reaction is carried out in an alkanoic carboxylic acid having from one to ten carbon atoms.
27. The process of claim 1 wherein a metal salt or oxide of palladium is used, said aromatic hydrocarbon compound is benzene and said reaction is carried out in acetic acid.
28. The process of claim 1 wherein a metal salt or oxide of palladium is used, said aromatic hydrocarbon compound is toluene and said reaction is carried out in an alkanoic carboxylic acid having from one to ten carbon atoms.
29. The process of claim 1 wherein a metal salt or oxide of palladium is used, said aromatic hydrocarbon compound is toluene and said reaction is carried out in acetic acid.
30. The process of claim 1 wherein a metal salt or oxide of copper is used, said aromatic hydrocarbon compound is benzene and said reaction is carried out in an alkanoic carboxylic acid having from one to ten carbon atoms.
31. The process of claim 1 wherein a metal salt or oxide of copper is used, said aromatic hydrocarbon compound is benzene and said reaction is carried out in acetic acid.
32. The process of claim 1 wherein a metal salt or oxide of copper is used, said aromatic hydrocarbon com pound is toluene and said reaction is carried out in an alkanoic carboxylic acid having from one to ten carbon atoms.
33. The process of claim 1 wherein a metal salt or oxide of copper is used, said aromatic hydrocarbon compound is toluene and said reaction is carried out in acetic acid.
metal is iridwherein said chloride ions chloride ions 34. The process of claim 1 wherein said metal is selected from the group consisting of cobalt, cerium, vanadium and manganese and said aromatic hydrocarbon compound carries from one to five alkyl substituents wherein the carbon adjacent to the aromatic hydrocarbon ring contains at least one hydrogen.
35. The process of claim 1 wherein said metal is selected from the group consisting of cobalt, cerium, vanadium and manganese and said aromatic hydrocarbon compound is toluene.
36. The process of claim 1 wherein at least two of said metals are employed, the first of which is selected from the group consisting of cobalt, manganese, vanadium and cerium and the second of which is selected from the group consisting of palladium and copper and the aromatic hydrocarbon compound carries from one to five alkyl substituents wherein the carbon adjacent to the aromatic hydrocarbon ring contains at least one hydrogen.
37. The process of claim 1 wherein at least two of said metals are employed, the first of which is manganese and the second of which is selected from the group consisting of palladium and copper and the aromatic hydrocarbon compound carries from one to five alkyl substituents wherein the carbon adjacent to the aromatic hydrocarbon ring contains at least one hydrogen.
38. The process of claim 1 wherein the reaction is carried out at a temperature of about 60 to about 150 C. and a pressure of about ten to about 1000 pounds per square inch gauge for about one to about ten hours, with the amount of halogen relative to the aromatic hydrocarbon, on a molar basis, being from about 2:1 to about 1:2, the amount of metal or salt or oxide thereof, on a molar basis, being from about 0.01 to about one percent, and the amount of nitrate, nitrite, NO or N0 on a molar basis, relative to the aromatic hydrocarbon being from about 1:3 to about 1:10
References Cited UNITED STATES PATENTS 2,152,357 3/1939 Moyer 260650 2,174,574 10 /1939 Farthing 260650X 3,145,237 8/1964 Van Helden et al. 260670 3,160,653 12/1964 Benning et al. 260650X 3,214,481 10/1965 Heinemann et al. 260650X 3,214,482 10/1965 Caropreso et a1. 260650X HOWARD T. MARS, Primary Examiner US. Cl. X.R.
260479R, 623H, 649, 649DP P040510 UNITED STATES PATENT OFFICE 56g CERTWQATE OF CORRECTION Patent No. 3s59l9645 Dated y 1971 Inventofls) Charles M. Selwitz It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
i I I Table III, Run No. 43, under "Product", "C H Br" should read C H Br".
Table III, Run No. 48, under "Product", "C H Cl" should read "C H Cl".
Table III, Run No. 49, under "Product", "C H Cl" should read "C H C1".
Table VIII, Run No. 98, under "Percent toluene" "7.89" should read "79.8".
Signed and sealed .this '{th day of December I 971 (SEAL) Attest:
EDWARD MELETGHERJR. ROBERT GOTTSCHALK Attesting Officer Acting Commissioner of Patents
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JP (1) | JPS4948417B1 (en) |
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FR (1) | FR2008869A6 (en) |
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1968
- 1968-05-20 US US730589A patent/US3591645A/en not_active Expired - Lifetime
-
1969
- 1969-05-09 DE DE19691923656 patent/DE1923656A1/en active Pending
- 1969-05-14 ES ES367231A patent/ES367231A2/en not_active Expired
- 1969-05-15 GB GB1229172D patent/GB1229172A/en not_active Expired
- 1969-05-16 NL NL6907552A patent/NL6907552A/xx unknown
- 1969-05-19 JP JP44038346A patent/JPS4948417B1/ja active Pending
- 1969-05-19 FR FR6916048A patent/FR2008869A6/fr not_active Expired
- 1969-05-20 BE BE733307D patent/BE733307A/xx unknown
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Also Published As
Publication number | Publication date |
---|---|
ES367231A2 (en) | 1971-04-01 |
NL6907552A (en) | 1969-11-24 |
BE733307A (en) | 1969-11-03 |
FR2008869A6 (en) | 1970-01-30 |
GB1229172A (en) | 1971-04-21 |
JPS4948417B1 (en) | 1974-12-21 |
DE1923656A1 (en) | 1970-09-10 |
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